Manufacture of sulphides of nitroaminodiphenyl or substitution products thereof



following general formula" Patented July 10, 1934 UNITED STATES PATENT OFFICE MANUFACTURE OF SULPHIDE AMINODIPHENYL on s U B s PRODUCTS THEREOF s or NIT TITU I 7 Robert Lantz, Paris, France, assignor of one-half to Socit Anonyme Des Matieres Colorantes & Produitsl Chimiques De Saint-Denis, Paris,

France No Draw ing. Application July 20, 193l, Serial No. A 552,067. In France August 8, 1930 24 Claims. (Grete -109') This invention relates to the manufacture. of

sulphides of nitroaminodiphenyl or substitution products thereof, which are represented by the duce an aminothiophenol according to the1 proc-.

ess described in my French patent application No. 299,805, filed August 1, 1930, and treating this aminothiophenol with l-:2- or 1:4.'chloronitrobenzene, or a substitution product thereof, which substitution product-may be identical with that (if any) used in the first instance or different therefrom. I There'is thus formed a condensation product of aminothiophenol in chloronitrobenzene,.namely a sulphide or a nitroaminodiphenyl.

The following equation expresses the reactions for: the simplest... case, in which the benzene nuclei do not contain substituents: I

It is advantageous to use in the first phase of the reaction a proportion of sulphur about that theoretically necessary for the transformation of the chloronitrobenzene into aminothiophenol, namely 2.5 molecules per molecule of the parent material. In most cases the chloronitrobenzene used'inthe secondrphase can be added directly to the liquid containing the product of the first phase, without-separating the last-named product. The final product is thus obtained in a particularly simple and economical manner. In.

. most cases the reaction may be conducted in aqueous medium without use of any other solvent. The invention permits easy manufacture of bodies which can otherwise be obtained only with difliculty. I I v u A number of new products has been made very easil'y by' theprocess of the invention, the yields being generally good. 5 In the examples which are here given by way of illustrating the invention sodium sulphide is used but soluble sulphides of other metals are also applicable. sulphide may be exchanged for the hydrosulphide or for a solution of sulphur in sodium sulphide.

ExampZe'1.A solution of 492 grams of crystallized sodium sulphide in 1230 cc. of water, to

Furthermore, a part of the sodiumwhich-has been added 123 grams of para-chloronitrobenzene, isb'oiled for 7 hours. After cooling, a saturated solution of zinc sulphate is added until adrop removed from-the liquid produces only a pale rose colour on paper dyed with brilliant orange. The white precipitate thus obtained is filtered and-redissolved in about 3 litres of hot water and 400 cc. of hydrochloric acid. The whole-is filtered at about the boiling point and then 100 grams of crystallized zinc sulphate and 900 grams of salt are added to the filtrate. The zinc compound of 4-aminothiophenol is thus pre-- cipitated in crystalline state.

9.25 grams of this dry compound are introduced,.together with 7.9 grams of .para-chloronitrobenzene into a solution consisting of 100 cc. of water and 10 cc. of caustic soda. solution of B. The whole is heated to-"boiling for about 4 hours. After removing the excess of cholornitrobenzene by a current of steam, the mixture is filtered. The crystalline product thus obtained is nearly'pure. sulphide iof 4-nitro-4-aminodiphenyl. f The yield is very good.

ExampZe'2.--A solution of 600 grams of crystallized sodium sulphidein 2500 cc. of water, to which 160 grams of l-chloro--nitrobenzene have been added,.is boiled'for about 10 hours. 7 A current of steam is then passed into the mixture until. nothing further is entrained thereby, and then there are added another 160 grams of l-chloro- 4-nitrobenzene and the boiling is continued for about 15 hours. The excess of chloronitrobene zeneis removed by a current of steam. The crystalline product which has been formed is filtered. It is very nearly pure sulphide of 4-nitro-4'- aminodiphenyl. It may be recrystallized from alcohol. The yield is almost theoretical.

fIn the second phase of the reaction'there may be substituted for .the 1-chloro-4-nitrobenzene, the 1-chloro-2-nitrobenzene or 1,4-dichloronitrobenzene, or 1-chloro-4-nitro-2 benzene-sulphonic acid, l-chloro-2-nitro-4-benzene-sulphonic acid or 1-chloro-4-nitro-2-benzene-carboxylic acid, or, 1-ch1oro-2,4-dinitro-benzene or the like. In analogous manner there may be used in the first phase of the reaction l-chloro-Z-nitrobenzene, 1,4-dichloro-Z-nitrobenzene, 1-ch1oro-4- nitro-2-benzene-sulphonic acid or the like.

In the following examples some of these reactions are illustrated.

Example 3.-A solution of 110 grams of sodium sulphide in 440 grams of water, to which has been added 27.3 grams of para chloronitrobenzene, is boiledfor 7 hours. I After passage of a current of nitrobenzene tufts of needles.

removed by steam and thewhole is filtered. After having brought the filtrate to the initial volume, there are added 196 grams of the sodium salt of lch1or0-4nitr0-2-benzene sulphonic acid. After boiling for 3 hours the product is salted out by addition of 20 per cent of common salt. It is filtered cold on the next day. This product is the crude sodium salt of 4'-nitro-2-amino-diphenylsulphide-Z-sulphonic acid.

The crystallized free acid is made by dissolving the sodium salt in water, filtering and precipitating by means of hydrochloric acid. The greenishyellowprecipitate consists of groups in and dried. It may be recrystallized from water.

'Earample 5.-'A solution of 164 grams of crys-,

tallized sodium sulphide in 30820 cc. of water containing 62.1 grams of the sodium para-nitrochlorobenzene-ortho-sulphonate, is boiled for 5 hours and therev are then added 40 grams of parachloronitrobenzene and the boiling is continued for 14 hours. The excess of chloronitrobenzene is removed by steam. On cooling, there is formed a precipitate of sodium -nitro-Q-aminodipheny1sulphide-2'-sulphonate. The motherliquor yields aconsiderable further quantity by salting out. The. free acid'maybe obtained in the crystalline state as described in Example 4.

- Example 6.A mixture of 7.85 grains of parachloronitrobenzene, 1.6 grams of sulphur and a solution of 24 grams of crystalline sodium su1-' phide in 75 cc. of Water; is boiled for 5 hours. After filtering there are added.3.'75 cc. of a caustic sodasolution of .40-B.. and then 7.85 grams of chloronitrobenzene, andthe Whole is boiled again fol-14 hours. The unaltered chloronitrobenzene is removed by steam and filtered. A product consisting of the sulphide of 4nitro-4'-aminodiphe nylis obtained.

Good results are also obtained if in this example there is substituted for the24 grams of crystallized sodium sulphide 12 grams of crystallized sodium sulphide and for the sulphur 3.4 grams of sodium hydrosulphide.

. There is appended hereto a table which indi-- cates the characteristics of a certain number of products, for the most part new, which have been manufactured in accordance with this invention.

TABLE Product No.1 Compound used inthe first phase: 1-chloro-4- Compound used in the second phase: l-chlorod-nitrobenzene Formula Appearance: Yellow leaflets Solvent used for crystallization: Alcohol Melting point: 143 C.

' Colors developed by naphthol: Red, insoluble The small quantity of chloraniline which is formed is then- It is Washed with fresh water;

Product No. 2

Compound used in the first phasez l-chlorod -nitrobenzene e Compound used in the second phase: l-chloro- 2-nitrobenzene Formula:

Appearance: Greenish yellow leaflets Solvent used for crystallization: Alcohol Melting point: 103C.

Colors developed by naphthol: Orange red insoluble calculated: 13 sulphur {found: 12.58

. calculated: 5.69

Diazotizable nitrogen y 5571 calculate-dailies KJeldahl nitrogen 0{ 11.1

Product No. 3

Compound used in the first phase: 1-chloro-4 nitrob'enzene 1 Compound used in the second phase: l-chloro- 2-nitro4 benzenesulphonic acid Formula:

Product No. 4

Compound used the first phase: l-chloro-i 13g nitrobenzene i Compound used in the second'phasez' I-chloro 4 nitro 2-benzene'-sulphonic acid Formula:

,. NHsOuQ Nos Appearanct-i: Free acid: yellow needles Solvent used for crystallization; Aqueous acetic acid Colors developed by naphthol: ,Orange red slightly soluble i455 jcalculated: 19.65 S l [found: 1 9.62

I lcal'culated: 4.29

Diazotizable nitrogen %1f.0und:4 25 15G Product No. ProductNo. 8

Compound used in the first phase: -1-ch1oro-4 Compound used in the first phase: l-chloro-2- nitrobenzene 1 nitrobenzene- H r c 5 Compound used in the second phase: l-chloro- Compound used in the second phase: 1 chloro-4 2,4 dinitrobenzene nitrobenzene Formula: a I 1 Formula: g

I110, Appearance: yellow prisms Solvent used for crystallization: alcohol Melting point: 874 C. 7 Colors developed by;naphthol: red orange insoluble Appearance: orange needles I r Y: Solvent used for crystallizaticm:v benzene Melting point: 168.5 C. Colors developed by naphthol: orange red in'.-.. soluble v a calculatedflis r {ca1cu1ated. 11 Sulphur %{f0und: .12; 7

found 10.3 I i 3 l. calculated: 5.69 jcalculated: 1 80 Diazotizable mtrogen%{ a Diazotizable nitrogen Hound: v found. 5.54

r I 1 I "calculated: 11.381

g Product No. 6 I v KJeldahl mtrogen Compound used in the first phase: l'echlpld-fi Y 7 a nitrobenzene a V V Y Prod ct No. 9 M Compound used 7 in the secondphase: '1-

chloro-4, nitro-2 benzoic acid ggag fig used t first P 14111019?- Formula: Compound luse'd in the second phase: l chlorozr-ni qbe ze el g Y T 1 NET-OS N01 Formula: Appearance: free acid: yellow; crystals I 1 r Solvent used for crystallization: sodiumsalt: I NH: r 40 hot water 7 a v x Appearanceg large yellow-leaflets Melting point. with decomposition to about s 01 vent used for crystallization: alcohol 0 0 13); levelo edb na hthol' orange ellow Melting point: 8214076 a y p J 5,-Colorsdeveloped by naphthol: orange yellow slightly soluble. r 1 b1 7 p i v p g g msoll e 7 7:

calculated: 11.05 V Sulphur {found:10.85 Sulphur %{:L g

calculated: 4.82 a a Diazotlzable mtrogen 434 A s I v Diazotizable {gg.ll iluatsec 5.69

g Product Q- 7 f a Product No. 10

p d used i the fi a Compound used in the fi rst phase: 1-chloronitrobenzene 2-nitrobenzene v C0mD011I 1d used In the Q d: pbasel Compound used in the second phase: l-chloro- Ch1OIO-2 mtrobenzene 2-nitro-4-benzenesulphonic acid Formula: V r Formula:

' o, NH, 7 N03 Appearance: yellow lamina v Appearance: sodium salt: orange yellow leaf- Solvent used for crystallization: alcohol lets r Melting point 133 C. Solvent used for crystallization: hotwater Colors developed by naphthol: red orange in- Colors developed by naphthol: orange yellow soluble soluble I 7o I Y calculated: 11 42 Y calculated: 18.4 sulphur {found: 11.42 Sulphur {found: 18.05

Diazotizable nitrogen %{ca1cu1ated:

calculated: 4.98

' found: 4.08

Diazotizable nitrogen 4 Sulphur Product NOkI-i Compound used in the first phase: 1-chloro- 2- nitrobenzene Compound used in the second phase? l-chlor'o- 4 nitro-z-benzene sulphonic acid v Formula:

Appearance: Free acid: clear yellow crystalline masses Solvent used for crystallization: hotwater Colors developed bynaphthol: orange yellow slightly soluble 4 [calculatedzl19i65 Sulphur lfound: 19.42

calculated: i 4,29 f0und:4.2 w

Product No. 12

Compound used in the first phase; l chloro-Z- nitrobenzene 1 1 Compound used in the second phase: l-chloro- Diazotizable nitrogen l-nitro 2-benzoic acid Formula: 7 Q I NHz coon Appearance: sodium salt: orange Solvent I sed for crystallization: hot-water Melting point of the acid: about 243 c;,wit1 i decomposition Colors developed by naphthol: orange yellow slightly soluble calculated 10.25 sulphur {found: 9.86 calculated: 4.48 found: 4.3 ProductNo,13 M Compound used in the first phase: l -chloro-4 Diazotizable nitrogen 45 nitro-2 benzene sulphonic acid Compound used in the second phase: l-chloro- 4 nitrobenzene Formula:

Formulaz 1 NH: I 102 I .7 Appearance: Large brown prisms Solvent used for crystallization: alcohol Melting point: 139 C.

Colors developed by naphthol calculated: 10.15

n stitution product WhatI claim is;

1. A method of preparing nitro-amino derivatives of diphenyl thio ethers; inwhioh the nitro and amino groups are attached to different nu clei and have, in their respective nuclei, any position but the meta-position in relation to. the sulphur, which comprises causing a chloronitroben-.

zene, with the exception of meta-chloronitrobenzene, to react with aneutral soluble salt of hydrogen sulphide, and then causing a ehl'oronitrobenzene with the'exception o'f meta-chloronitrobenzene, to react on the product of the first reaction.

2. A method of preparing sulphides "of nitroaminodiphenyl according 1 to claim 1 wherein the reactions are conducted in anaqueous medium.

3. A method of preparing sulphides of 'nitro-'' aminodiphenyl according to claim 1 in which the portion of the neutral soluble sulphide is replaced by the corresponding disulphide.

4. A method of preparing sulphides of nitroaminodipheriyl"according to claim 1 inwhich the:

portion of the neutral soluble sulphide is replaced Q by the corresponding hydrosulphide.

5. A method of preparing nitro-amino derivatives of diphenyl thio ethers, in which the nitro andam'ino groups are attached to difierent nuclei and have, in their respective nuclei, any position but the meta-position in relation to the sulphur, which comprises causing a chloronitro benzene, with the exception of meta-chloronitrobenzene, to reactwith a neutral soluble salt of hydrogen sulphide, and then causing a substitution product ofchloronitrobenzene, other than meta-chloronitrobenzene, to react on the product of the first reaction.

6. A method. ofv preparing nucleal substitution product .of sulphid'es'of nitroaminodiphenyl according to claim 5 ducted in an aqueous medium.

'7. A method of preparing nucleal substitutionproducts of: sulphides of nitroaminodiphenyl ac- I cording to claim 5 in which the portion of the neutral soluble sulphide is replaced by the corresponding disulphide. I) f 8. A method of preparing-nucleal substitution products of sulphides of nitroamino diphenyl according touclaim5 in' which the portionof the neutral soluble sulphideu'is replaced'by the corresponding hydrosulphide.

9. A method ofgpreparlng:nitroamino derivatives of diphenyl thio ethers, in which the nitro andamino groups are attached to different nuclei and have, in their respective nuclei, anyposition ;but. the meta-position in relation to the sulphur, which comprises causing a nuclealrsubof chloronitrobenzene; other than meta-chloronitrobenzene, to react with a neutral soluble-saltpf hydrogensulphide and then causing chloronitrobenzene, other than meta-chloronitrobenzene, to react on the product of the first reaction.

10. A method of preparing substitution products of sulphides of nitrojaminodiphenyl according to claim 9 'in' which the reactions are conducted in an aqueous medium.

11. A method of "preparing nucleal" substitution I 1 products of sulphides of nitroaminodiphenyl ac cording to claim 9 in ;which the portion of the neutral soluble sulphide is rep laced by the corresponding disulphide.

12. A method of preparing nucleal substitution I 5 products of sulphides pf nitroaminodiphenyl'"-according to claim 9 in which the portion of neutral in which the reactions are con soluble sulphide is replaced by the corresponding hydrosulphide.

13. A method of preparing nitroamino derivatives of diphenyl thio ethers, in which the nitro and amino groups are attached to difierent nuclei and have, in their respective nuclei, any position but the meta-position in relation to the sulphur, which comprises causing a nucleal substitution product of chloronitrobenzene, other than parachloronitrobenzene, to react on the neutral soluble salt of hydrogen sulphide and then causing the substitution product of chloronitrobenzene, other than meta-chloronitrobenzene, to react on the product of the first reaction.

i i. A method of preparing a nucleal substitution product according to claim 13 in which the reactions are conducted in an aqueous medium.

15. A method of preparing a nucleal substitution product of sulphides of nitroaminodiphenyl according to claim 13 in which the portion of the neutral soluble sulphide is replaced by the corresponding disulphide.

16. A method of preparing a nucleal substitution product of sulphides of nitroaminodiphenyl according to claim 13 in which the portion of the neutral soluble sulphide is replaced by the corresponding hydrosulphide.

17. A method of preparing sulphides of nitro aminodiphenyl, according to claim 1 in which the second reaction is conducted in the liquid in which the first reaction has been produced without separating the product of the'last named reaction.

18. A method of preparing nucleal substitution products of sulphides of nitroaminodiphenyl according to claim 5 in which the second reaction is conducted in the liquid in which the first reaction has been produced without separating the product of the last named reaction.

19. A method of preparing nucleal substitution products of sulphides of nitroaminodiphenyl according to claim 9 in which the second reaction is conducted in the liquid in which the first reaction has been produced without separating the product of the last named reaction.

20. A method of preparing a nucleal substitution product of sulphides of nitroaminodiphenyl according to claim 13 in which the second reaction is conducted in the liquid in which the first reaction has been produced without separating the product of the last named reaction.

21. A body whose formula is whose sodium salt has the appearance of orange yellow needles, and prisms, adapted to be dissolved for crystallization in aqueous alcohol, and adapted to give a slightly soluble orange red dye with naphthol.

22. A body whose formula is NHi N02 whose sodium salt has the appearance of orange yellow leaflets, adapted to be dissolved for crystallization in hot water, adapted to give a slightly soluble orange dye with naphthol.

23. A body whose formula is NHz OOH meta position in relation to the sulphur, said 1 sulphide further consisting of a salt forming acid radical selected from the group consisting of COOH and SOaH.

ROBERT LANTZ. 

